Field of the Invention
[0001] The present invention relates to the production of a magnetic recording medium with
improved magnetic properties comprising a substrate and, as a recording layer, a ferromagnetic
metal thin layer containing oxygen atoms.
Background of the invention
[0002] Generally, a magnetic recording medium comprising a ferromagnetic metal thin layer
as a recording layer is produced by vacuum deposition of ferromagnetic metal or an
alloy containing it on a substrate such as a plastic film with travelling it around
a peripheral surface of a cylindrical can installed in a vacuum deposition apparatus.
To produce the magnetic recording medium with improved magnetic properties, the vaporized
ferromagnetic metal is obliquely impinged on the substrate and simultaneously oxydizing
gas is jetted into a stream of the vaporized metal near a position at which the vaporized
metal is impinged on the substrate at the maximum impinging angle (cf. Japanese Patent
Kokai Publication (unexamined) Nos. 41442/1983 and 83328/1983) or at the minimum impinging
angle (cf. Japanese Patent Kokai Publication (unexamined) Nos. 41443/1983 and 83327/1983).
DE-A-32 41 775 discloses a magnetic recording medium with a comparable oxygen distribution
in the ferromagnetic thin film layer.
[0003] In the former method, however, the magnetic properties are not satisfactorily improved.
Particularly, improvement of coercive force of the recording medium greatly depends
on the deposition rate. As the deposition rate increases, a concentration of oxygen
atom contained in the ferromagnetic metal thin layer increases in an interfacial layer
adjacent to the substrate and decreases from the interfacial layer to the surface
of the thin layer. Therefore, the effect of the contained oxygen atom is not effectively
exerted and it is difficult to produce the magnetic recording medium with the improved
magnetic properties at such a high deposition rate as is suitable for mass production.
[0004] Japanese Patent Kokai Publication (unexamined) No. 83327/1983 describes that the
latter method provides a magnetic recording medium in which the concentration of oxygen
atom contained in the ferromagnetic metal thin layer gradually increases from the
interfacial layer to the surface. According to the study by the present inventors,
in the magnetic recording medium produced by said method, the concentration of oxygen
atom contained in the ferromagnetic metal thin layer decreases from the interfacial
layer to the surface. Since the degree of decrease of the oxygen atom concentration
is smaller than the former method, although the effect of the contained oxygen atom
is not so seriously deteriorated as in the former method, still improvement of the
magnetic properties is not satisfactory. Particularly, it is also difficult to produce
the magnetic recording medium with the improved magnetic properties at such a high
deposition rate as is suitable for mass production.
[0005] Japanese Patent Kokai Publication (unexamined) No. 37843/1983 a method to improve
the efficiency of diagonal vapor deposition and to obtain a magnetic recording medium
of improved coercive force by passing gaseous oxygen in larger amount, in a region
of a smaller incident angle than in a region of a larger incident angle in the vapor
depositing region where a vapor depositing material is blown to a substrate.
[0006] In a vacuum vessel, a non-magnetic substrate is taken up from a roller onto a take-up
roller via guiding roller. A vapor deposition material is disposed in the lower part
of the vessel, and is heated to evaporate by a heating means, and is vapor-deposited
at a prescribed incident angle on the surface of the substrate, whereby a ferromagnetic
thin film is formed. A pipe provided with a nozzle is provided in thevapordepos- iting
region, and oxygen flow is passed from the part where the incident angle of vapor
deposition particles is small to the part where said angle is large. By this oxygen
flow the evaporating particles are diffused from the region of a smaller incident
angle to the region of a larger incident angle. By such method, the magnetic recording
medium having improved coercive force is obtained.
Summary of the invention
[0007] One object of the invention is to provide a magnetic recording medium with improved
magnetic properties.
[0008] Another object of the invention is to provide a magnetic recording medium comprising
a ferromagnetic metal thin layer as a recording layer with high coercive force and
small magnetic domain.
[0009] Further object of the invention is to provide a magnetic recording medium with improved
distribution of oxygen atom concentration in the ferromagnetic metal thin layer.
[0010] Still another object of the invention is to provide an improved method for producing
a magnetic recording medium comprising a ferromagnetic metal thin layer as a recording
layer with a high coercive force and small magnetic domain, which method comprises
obliquely impinging a vaporized ferromagnetic metal on a substrate and simultaneously
jetting oxydizing gas on the substrate.
[0011] According to the present invention, there is provided a magnetic recording medium
comprising a substrate and, as a recording layer, a ferromagnetic metal thin layer
formed on the substrate by deposition, in which the ferro-magnetic metal thin layer
contains oxygen atoms in such a manner that concentrations of oxygen atom in a surface
layer and an interfacial layer adjacent to the substrate are higher than that in an
intermediate layer between the surface and interfacial layers, whereby the magnetic
domain is made extremely small and the coercive force is greatly increased.
[0012] Further, there is provided a method for producing a magnetic recording medium of
the invention, which comprises impinging a ferromagnetic metal material at an oblique
impinging angle on a substrate with travelling it around a peripheral surface of a
cylindrical can from a point at which the stream of the vaporized metal material is
impinged at a high impinging angle to a point at which the stream is impinged at a
low impinging angle, and simultaneously jetting an oxydizing gas directly onto the
substrate, wherein an angle between the stream of the oxydizing gas and that of the
vaporized ferromagnetic metal material is not greater than 30° and a central angle
about the longitudinal axis of the cylindrical can of the directly jetted arc area
of the substrate starting from the minimum impinging angle point toward a point at
which the impinging angle is greater is not greater than 10°, characterized in that
the oxygen gas is supplied to the substrate at the impinging angle point (A) and further
jetting an oxydizing gas directly into the substrate at least at the maximum impinging
angle point from a direction which does not intersect the stream of the vaporized
ferromagnetic metal and a central angle about the longitudinal axis of the cylindrical
can of the directly jetted arc area of the substrate starting from the maximum impinging
angle point toward a point at which the impinging angle is not greater than 20°.
Brief description of the drawings
[0013]
Fig. 1 is a schematic sectional view of a vacuum deposition apparatus suitable for
practicing the method of the present invention,
Fig. 2 is an enlarged sectional view of the main part of the apparatus of Fig. 1,
Fig. 3 is a schematic sectional view of anotherva- cuum deposition apparatus suitable
for practicing the modified method of the present invention,
Fig. 4 is an enlarged sectional view of the main part of the apparatus of Fig. 3,
Figs. 5 and 6 are each a schematic view of a vacuum deposition apparatus for producing
a conventional magnetic recording medium,
Fig. 7 shows the distributions of the oxygen atom concentration in the ferromagnetic
metal thin layers of the magnetic recording mediums produced in Examples and Comparative
Examples,
Fig. 8 shows relationships between the coercive force and the average oxygen atom
concentration of the magnetic recording mediums produced in Examples and Comparative
Examples, and
Fig. 9 shows relationships between the size of magnetic domain and the average oxygen
atom concentration of the magnetic recording mediums produced in Examples and Comparative
Examples.
Detailed description of the invention
[0014] The present invention is based on the study of the relationship between the distribution
of the oxygen atom concentration through the thickness of the ferromagnetic metal
thin layer and magnetic properties of the recording medium. In the conventional ferromagnetic
metal thin layer in which the oxygen atom concentration decreases from the interfacial
layer adjacent to the substrate toward the surface layer, although the oxygen atom
concentration is high in the interfacial layer in which the magnetic interaction is
weak due to large distance between the magnetic particles caused by a shadow effect
of the oblique impingement, the oxygen atom concentration is low in the surface layer
in which the magnetic interaction is strong due to narrow distance between the subsequently
grown magnetic particles. Therefore, the effect of the contained oxygen atom is not
effectively exerted so that the high coercive force and good magnetic properties are
not achieved. However, the oxygen atom concentration in the interfacial layer of the
ferromagnetic metal thin layer is controlled by supplying an enough amount of oxygen
when nuclei of the magnetic particles are formed at the maximum impinging angle point
and thereby the size of the slantingly grown particle in a curved pillar shape can
be reduced. In addition, if the oxygen atom concentration in the surface layer in
which the magnetic interaction is strong is made higher than that in an intermediate
layer between the interfacial and surface layers, non-magnetic oxides are formed in
the surface layer and the magnetic interaction is suppressed. Therefore, the effect
of the contained oxygen atom is effectively exterted so that the magnetic domain size
further minimized, and the magnetic properties are much improved.
[0015] In the specification, the surface layer of the ferromagnetic metal thin layer is
intended to mean a surface layer which contains oxygen atoms which are supplied by
jetting the oxydizing gas and chemically bound to the ferromagnetic metal and to exclude
a contaminated layer.
[0016] The oxygen atom concentration in the ferromagnetic metal thin layer is lowest in
its intermediate layer. That in the surface layer is 1.5 to 6.0 times that in the
intermediate layer, and that in the interfacial layer is 1.2 to 3.0 times that in
the intermediate layer. The oxygen atom concentration in the ferromagnetic metal thin
layer is lowest in its intermediate layer. That in the surface layer is 1.5 to 6.0
times that in the intermediate layer, and that in the interfacial layer is 1.2 to
3.0 times that in the intermediate layer. The oxygen atom concentration in the intermediate
layer is from 5 to 15% of the total number of all component atoms contained in the
intermediate layer, and that in the whole ferromagnetic metal thin layer is from 10
to 30% of the total number of the component atoms contained in the whole layer. When
the oxygen atom concentrations are in these ranges, the magnetic recording medium
has the coercive force not lower than 63.6 kA/m (800 oersted) and the magnetic domain
not greater than 0.3 µm. If the oxygen atom concentration in the interfacial layer
is less than the above range, is is dificult to sufficiently reduce the size of the
ferromagnetic metal particle which forms a nucleus. If the oxygen atom concentration
in the surface layer is less than the above range, the non-magnetic oxide around the
metal particles are not developed enough to obtain high coercive force and to reduce
the size of the magnetic domain. If the oxygen atom concentration either in the interfacial
or surface layer is higher than the above range, the magnetic properties may change
for the worse.
[0017] In the specification, the whole ferromagnetic metal thin layer is intended to mean
a layerwhich contains oxygen atom which is supplied by jetting the oxydizing gas and
bound with the ferromagnetic metal and to exclude a skin layer contaminated by oxygen
liberated from organic material or migrated from air.
[0018] The magnetic recording medium is produced by a method according to claims 1 and 2.
[0019] In the present invention, specific examples of the substrate are a plastic film made
of a generally used polymer such as polyesters (eg. polyethylene terephthalate, etc.),
polimides, polyamides, etc. and a metallic film made of a non-magnetic metal such
as copper.
[0020] Specific examples of the ferromagnetic metal material are a ferromagnetic metal such
as Co, Ni, Fe, etc., their oxides, an alloy containing at least one of them and their
compounds such as Co-P, Co-Ni-P, etc.
[0021] The present invention will be illustrated by reference to the accompanied drawings
by way of example.
[0022] Fig. 1 is a schematic sectional view of an embodiment of a vacuum deposition apparatus
suitable for practicing the method of the invention in which the oxydizing gas is
jetted on the substrate at or near the minimum impinging angle position. A vacuum
chamber 1 is kept in vacuo by means of an evacuating system 2. Acylindrical can 3
is installed in the central part of the apparatus 1, and a substrate 4 such as a plastic
film is unwound from a roll 5, guided by a guide roll 6 and travelled around the peripheral
surface of the cylindrical can 3. Then, it is guided by another guide roll 7 and wound
by a wind-up roll 8. Beneath the cylindrical can 3, a heating vessel 9 is placed,
in which a ferromagnetic metal material 10 is contained and heated to vaporize. The
vapor of t he material 10 is obliquely impinged on the substrate 4 by means of a deposition-preventing
plate 11 placed between the cylindrical can 3 and the vessel 9. Simultaneously with
deposition of the material 10, an oxydizing gas is jetted on the substrate 4 at least
at a minimum impinging angle point A from a gas inlet nozzle 12 placed between the
can 3 and the plate 11.
[0023] As shown in Fig. 2, the position ofthe nozzle 12 is so selected that the distance
D from the supply opening 12a to the position A is not longerthan 15 cm and the angle
a between the stream of the oxydizing gas and the stream B of the vaporized metal
material impinged by the minimum impinging angle 0 is not greater than 30°. Further,
the central angle β about the longitudinal axis O of the cylindrical can 3 of the
directly jetted arc area E of the substrate starting from the minimum impinging angle
point A toward a point at which the impinging angle is greater is not greater than
10°. When the oxydizing gas is jetted on the substrate at least at the minimum impinging
angle point A under such conditions, the concentration of oxydizing gas is maximum
near the point A and, in addition, oxygen filled in the chamber 1 is tend to be trapped
in the ferromagnetic metal thin layer in a relatively high concentration near the
maximum impinging angle point C since the deposition rate of the ferromagnetic metal
material is lower near the point C. As the result, in one hand, when the nuclei of
the particles of the ferromagnetic material are formed on the substrate 4 near the
point C, particles having a sufficiently small size and containing comparatively large
amount of oxygen atom are formed. On the other hand, particles are suitabley grown
near the point A due to rich oxygen and the deposited ferromagnetic metal material
contains a sufficient amount of oxygen atom at a part in which magnetic interaction
increases as the particles grow to form a ferromagnetic metal thin layer having a
small magnetic domain and high coercive force. In the thus formed ferromagnetic metal
thin layer, since the oxygen atom concentration in the interfacial layer and that
in the surface layer are high, magnetization tends to direct in a direction perpendicular
to the substrate, which is suitable for high density recording, and the distribution
of the oxygen atom concentration is idealized, that is, the oxygen atom concentration
in the intermediate layer is lowest and that in the interfacial layer is higher than
that in the intermediate layer and lower than that in the surface layer. Thereby,
the magnetic recording medium having improved magnetic properties is produced.
[0024] Since a large amount of the oxydizing gas is jetted at least at the minimum impinging
angle point A, oxygen atoms are trapped by the ferromagnetic metal material in a higher
concentration and the coercive force is more increased as the deposition site is increased.
Therefore, the magnetic recording medium having sufficiently improved magnetic properties,
for example, the magnetic domain of not larger than 0.3 micron can be produced under
conditions suitable for mass production, that is, under the conditions in which the
minimum impinging angle of the vaporized ferromagnetic metal material is not greater
than 60° and the deposition rate is not lower than 100 nm/sec (1,000 A/sec). If the
minimum impinging angle of the vaporized material is greater than 60°, the efficiency
of deposition is deteriorated and unsuitable for the mass production. In addition,
any impinging disturbance between the oxydizing gas and the vaporized ferromagnetic
metal material hardly occur, and the impinging angle is not fluctuated, which is often
found in the conventional method comprising jetting the oxydizing gas into the stream
of the vaporized ferro- magnetic metal material.
[0025] Fig. 3 shows another vacuum deposition apparatus suitable for practicing the improved
method of the invention. This apparatus has substantially the same construction as
that of Fig. 1 except that the apparatus of Fig 3 further comprises a gas inlet tube
13 near the maximum impinging angle point C and the oxydizing gas is jetted from the
nozzle 13 on the substrate near the point C.
[0026] As shown in Fig. 4, the position of the nozzle 13 is so selected that the distance
H from the supply opening 13a to the position C is not larger than 50 cm, and the
central angle y about the longitudinal axis O of the cylindrical can 3 of the directly
jetted arc area F of the substrate starting from the maximum impinging angle point
C toward a point at which the impinging angle is smaller is not greater than 20°.
In the apparatus of Fig. 3, since the oxydizing gas is jetted from the nozzle 13 on
the substrate near the maximum impinging angle point C, the size of the particle nucleus
of the ferromagnetic metal is more easily controlled to obtain smaller particle, and
oxygen atom is trapped in the interfacial layer in a higher concentration.
[0027] As the oxydizing gas, pure oxygen gas or a mixture of oxygen and diluent gas (eg.
nitrogen, etc.) is preferably used.
[0028] The present invention will be hereinafter explained further in detail by following
Examples.
Example 1
[0029] The vacuum deposition apparatus of Fig. 1 installed with the cylindrical can 3 of
60 cm in diameter was used. A base film 4 of polyethylene terephthalate was travelled
around the peripheral surface of the rotating cylindical can 3 through the guide roll
6 and wound by the wind-up roll 8 through the guide roll 7. On the other hand, an
alloy 10 of cobalt and nickel in a weight ratio of 8:2 was charged in the vessel 9.
Then, the chamber 1 was evacuated by the system 2 to a pressure of about 6.66 mPa
5xl 0-5 torr). and the alloy was heated to evaporate and obliquely impinged on the
substrate with the minimum impinging angle of 50° at the deposition rate of 80 nm/sec
(800 A/sec). Simultaneously, the oxygen gas was jetted from the nozzle 12 on the film
4 at the minimum impinging angle point A with varying the oxygen pressure in the chamber.
The distance D between the opening 12a of the nozzle 12 and the point Awas 5cm, and
the angle and direction of the oxygen gas was so selected that the angle a was 20°
and the angle β was 10°. In this manner, the ferromagnetic metal thin layer containing
the Co-Ni alloy was formed on the base film 4 and cut in the form of plural magnetic
recording tapes each having the predetermined width.
Example 2
[0030] In place of the apparatus used in Example 1, the vacuum deposition apparatus of Fig.
3 was used, and the ferromagnetic metal thin layer was formed on the base film in
the same manner as in Example 1 except that the oxygen gas was also jetted from the
nozzle 13 on the base film 4 atthe maximum impinging angle point C with varying the
pressure of the jetted gas, and plural magnetic recording tapes were produced. The
distance H between the opening 13a of the nozzle 13 and the point C was 15 cm, and
the angle and direction of the oxygen gas was so selected that the angle y was 20°.
Comparative Example 1
[0031] In place of the apparatus used in Example 1, the apparatus of Fig. 5 was used, which
has substantially the same construction as that of Fig. 1 exceptthatthe gas inlet
nozzle 14 was placed between the cylindrical can 3 and the plate 11 in place of the
nozzle 12 so that the gas was jetted in the direction shown by the arrow into the
stream B of the vaporized ferro- magnetic metal material but not directly on the base
film 4. In this manner, the ferromagnetic metal thin layer was formed on the base
film, and plural magnetic recording tapes were produced.
Comparative Example 2
[0032] In place of the apparatus used in Example 1, the apparatus of Fig. 6 was used, which
has substantially the same construction as that of Fig. 1 exceptthatthe gas inlet
nozzle 15 was placed near the maximum impinging angle point C in place of the nozzle
12 so that the gas was jetted in the direction shown by the arrow into the stream
B of the vaporized ferromagnetic metal material but not directly on the base film
4. In this manner, the ferromagnetic metal thin layer was formed on the base film
and plural magnetic recording tapes were produced.
[0033] The magnetic recording tapes produced in Exam- pies and Comparative Examples under
the constant oxygen pressure of 0.26 Pa (2x10-
4 torr.) were examined for distribution of oxygen atom concentration with an Auger
electron spectrometer. The results are shown in Fig. 7, in which Curves A, B, C and
D correspond to the tapes produced in Example 1, Example 2, Comparative Example 1
and Comparative Example 2, respectively.
[0034] A is dear from these results, while, in the recording tapes produced in Comparative
Examples, oxygen atom was contained in the ferromagnetic metal thin layer with gradually
decreasing concentration from the interfacial layer to the surface layer, in the recording
tapes produced in Examples, oxygen atom concentration was highest in the surface layer,
next highest in the interfacial layer and lowest in the intermediate layer.
[0035] The coercive force and the magnetic domain size were measured of the magnetic recording
tapes produced in Examples and Comparative Examples. The results are shown in Figs.
8 and 9.
[0036] Fig. 8 shows the relationship between the coercive force and the average oxygen atom
concentration in the whole ferromagnetic metal thin layer. Curves A to D correspond
to the tapes produced in Example 1, Example 2, Comparative Example 1 and Comparative
Example 2, respectively.
[0037] Fig. 9 shows the relationship between the size of the magnetic domain and the average
oxygen atom concentration in the whole ferromagnetic metal thin layer. Curves A to
D correspond to the tapes produced in Example 1, Example 2, Comparative Example 1
and Comparative Example 2, respectively.
[0038] As is seen from the results shown in Figs. 8 and 9, the magnetic recording tapes
of the invention produced in Examples had high coercive force and smaller magnetic
domain than those produced in Comparative Examples.
[0039] While the coercive force of the magnetic recording tape produced by the conventional
methods is 55.6 kA/m (700 oersted) or less and its magnetic domain is 0.5 µm or larger,
the coercive force of the magnetic recording tape of the invention is not lower than
63.6 kA/m (800 oersted), particularly up to 79.5 kA/m (1,000 oersted) and its magnetic
domain is not larger than 0.3 µm.
1. Verfahren zur Herstellung eines magnetischen Aufzeichnungsmediums, das ein Substrat
(4) und als Aufzeichnungsschicht eine dünne Schicht aus einem ferromagnetischen Metall
umfaßt,
worin die dünne Schicht aus dem ferromagnetischen Metall eine Konzentration der Sauerstoff-Atome
in einer Oberflächenschicht der Metallschicht und in einer dem Substrat benachbarten
Grenzschicht aufweist, die höher ist als diejenige in einer Zwischenschicht zwischen
der Oberflächen- und der Grenzschicht, und worin die Konzentration der Sauerstoff-Atome
in der Oberflächenschicht 1,5- bis 6,0-mal so hoch ist wie diejenige in der Zwischenschicht
und die Konzentration der Sauerstoff-Atome in der Grenzschicht 1,2 bis 3,0-mal so
hoch ist wie diejenige in der Zwischenschicht,
worin die Konzentration der Sauerstoff-Atome in der Zwischenschicht 5 bis 15 % der
Gesamtzahl der Atome aller in der Zwischenschicht enthaltenen Komponenten beträgt
und die Konzentration der Sauerstoff-Atome in der gesamten dünnen Schicht aus dem
ferromagnetischen Metall 10 bis 30 % der Gesamtzahl der Atome der in der gesamten
Schicht enthaltenen Komponenten beträgt, wobei die dünne Schicht aus dem ferromagnetischen
Metall eine Koerzitivkraft, die nicht niedriger als 63.6 kA/m (800 Oersted) ist, und
magnetische Bezirke, die nicht größer als 0,3 µm sind, besitzt,
wobei das Verfahren
das Aufprallen-Lassen eines ferromagnetischen metallischen Materials (10) unter einem
schrägen Auftreff-Winkel auf ein Substrat (4), während dieses um die Umfangsoberfläche
einer zylindrischen Trommel (3) von einem Punkt, bei dem der Strom des verdampften
metallischen Materials unter einem großen Auftreff-Winkel aufprallt, zu einem Punkt,
bei dem der Strom unter einem kleinen Auftreff-Winkel aufprallt, bewegt wird, und
gleichzeitig das Einblasen eines Strahls eines oxidierenden Gases (12) unmittelbar
in das Substrat hinein umfaßt, wobei der Winkel (a) nicht größer als 30° ist zwischen
dem Strom des oxidierenden Gases und demjenigen des verdampften ferromagnetischen
metallischen Materials, das im Punkt (A) des minimalen Auftreff-Winkels aufgetroffen
ist, und ein zentraler Winkel (ß) nicht größer als 10° ist um die Längsachse der zylindrischen
Trommel (3) der Fläche des direkt von dem Strahl bestrichenen Bogens des Substrats
(4) ausgehend von dem Punkt (A) des minimalen Auftreff-Winkels zu einem Punkt umfaßt,
bei dem der Auftreff-Winkel größer ist, dadurch gekennzeichnet, daß das Sauerstoff-Gas
dem Substrat an dem Punkt (A) des minimalen Auftreff-Winkels zugeführt wird.
2. Verfahren nach Anspruch 1, weiterhin umfassend das Einblasen eines Strahls eines
oxidierenden Gases unmittelbar in das Substrat hinein wenigstens an dem Punkt (C)
des maximalen Auftreff-Winkels aus einer Richtung, die den Strom des ferromagnetischen
Metalls nicht schneidet, wobei ein zentraler Winkel (y) nicht größer als 20° ist,
um die Längsachse der zylindrischen Trommel der Fläche des direkt von dem Strahl bestrichenen
Bogens des Substrats ausgehend von dem Punkt (C) des maximalen Auftreff-Winkels zu
einem Punkt, bei dem der Auftreff-Winkel kleiner ist.